The novel 3D octahedron-like PbF 2 structures with dimension of 2–4 µm have been successfully synthesized by a simple route at low temperature. The morphologies and structures of as-prepared products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The growth mechanism has been proposed for octahedral PbF 2 . It was found that the aging time is important for the formation of 3D octahedron-like PbF 2 structures. The room-temperature photoluminescence measurements revealed a strong blue emission band at 485 nm. It was indicated that the as-prepared octahedral PbF 2 could have the potential application in optoelectronic devices.